EP3380561A1 - Säuredestabilisierung von elastomerer dachverkleidung - Google Patents

Säuredestabilisierung von elastomerer dachverkleidung

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Publication number
EP3380561A1
EP3380561A1 EP16816476.2A EP16816476A EP3380561A1 EP 3380561 A1 EP3380561 A1 EP 3380561A1 EP 16816476 A EP16816476 A EP 16816476A EP 3380561 A1 EP3380561 A1 EP 3380561A1
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EP
European Patent Office
Prior art keywords
component
acid
composition
aqueous
monomer
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Granted
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EP16816476.2A
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English (en)
French (fr)
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EP3380561B1 (de
Inventor
Joe MALLARDI
Charles J. Rand
Janah C. Szewczyk
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Rohm and Haas Co
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Rohm and Haas Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D7/00—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C

Definitions

  • the present invention relates to two-component aqueous compositions for coating roofing substrates comprising, in one component having a pH of from 7.5 to 10, (i) one or more emulsion copolymers having a glass transition temperature (Tg) of from -45°C to 0°C and (ii) one or more anionic surfactants, and, in a separate component, (iii) an aqueous (poly)carboxylic acid or polymeric polyacid, preferably, a (poly)carboxylic acid.
  • Tg glass transition temperature
  • VOC volatile organic compound
  • the Plastiroute is the closest art but is limited to horizontal traffic markings. This is a different Tg range and different coating composition. US5985366A is the closest to the application (ie roof coatings) but requires raising the pH (ie pH stabilizing as they call it) and intentionally has only a surface quick setting film as they want the material underneath to dry normally.
  • U.S. Patent no. 5,985,366, to Wright et al. discloses sprayable roof coatings wherein a catalyst having a charge opposite that of the emulsion polymer roof coating is sprayed on top of an applied roof coating.
  • Wright stabilizes the emulsion polymer pH, for example, to 10.75 or higher prior to use to make it cationic and then, after applying the emulsion polymer, sprays on acid as a topical application catalyst, meaning that the emulsion polymer has to have a fairly high acid salt, amine or base concentration to insure acid curing of the top of the applied emulsion copolymer layer.
  • Wright discloses intentionally allowing the emulsion polymer coating underneath the spray to coagulate.
  • the methods in Wright would not allow for a high film build or single application roof coating because the emulsion copolymer coating materials in the applied coating layer do not dry underneath the acid treated top of the coating fast enough to enable the making of a coating thick enough to serve as a useful roof coating.
  • the methods in Wright are useful only to insure early rain resistance of the top of an applied coating layer and do not achieve coating layer through cure.
  • the present inventors have endeavored to provide aqueous compositions and methods of using them in making roof coatings having an instantaneous or very rapid set that can be applied to a desired film build in one application.
  • two-component aqueous compositions for coating roofing substrates comprise, in a component one that has a pH of from 7.5 to 10, or, preferably, 9.1 or less, or, more preferably, less than 8.6, (i) one or more emulsion copolymers having a glass transition temperature (Tg) as determined by differential scanning calorimetry (DSC) of from -45°C to 0°C, preferably, from -35°C to -10°C, (ii) one or more anionic
  • surfactants and, in a separate component, (iii) an aqueous acid chosen from a (poly)carboxylic acid or polymeric polyacid, preferably, a (poly)carboxylic acid, preferably, acetic acid,
  • component one of the two-component aqueous composition comprises less than 0.15 wt.%, for example, from 0.001 to 0.1 wt.%, or, preferably, less than 0.095 wt.%, or, more preferably, less than 0.09 wt.% of ammonia, all weights based on the total weight of the component one composition.
  • each of the (i) one or more emulsion copolymers has a weight average molecular weight of from 50,000 to 2,000,000 or, preferably, from 150,000 to 500,000.
  • At least one of the (i) one or more emulsion copolymers comprises, in copolymerized form, a monomer mixture of (a) from 60 wt.% to 94 wt.%, preferably, 65 wt.% or more, or, preferably, up to 93.75 wt.% of one or more soft monomer, such as a C4 to C24 alkyl (meth)acrylate, for example, butyl acrylate or ethyl hexyl acrylate, (b) from 6.0 to 35 wt.%, preferably, 29.75 wt.% or less, or, preferably, up to 20 wt.%, of one or more hard vinyl monomers, such as a Ci to C3 alkyl (meth)acrylate, (meth) acrylonitrile or a vinyl aromatic monomer, preferably, methyl methacrylate (MMA) or acrylonitrile (AN),
  • At least one of the (i) one or more emulsion copolymers comprises, in copolymerized form, a monomer mixture of 19.5 wt.% or less or, preferably, 10 wt.% or less, or, more preferably, 5 wt.% or less of any vinyl aromatic monomer, such as styrene; and, further wherein, the monomer mixture comprises 1 1 wt.% or less or, preferably, 8 wt.% or less of (meth)acrylonitrile, all monomer wt.%s based on the total solids in the monomer mixture.
  • At least one of the (i) one or more emulsion copolymers comprises, in copolymerized form, from 0.1 to 2 wt.%, based on the total solids in the monomer mixture, of an adhesion promoting ethylenically unsaturated monomer (e), such as a ureido functional (meth)acrylate.
  • an adhesion promoting ethylenically unsaturated monomer (e) such as a ureido functional (meth)acrylate.
  • the one component further comprises one or more pigments, extenders, fillers or mixtures thereof, and has a pigment volume concentration (%PVC) of from 20 to 55 or, preferably, from 30 to 50, or, more preferably, 35 to 45.
  • %PVC pigment volume concentration
  • the component one further comprises one or more hydrophilic polymeric dispersant, such as a polymethacrylic acid; in one example, the hydrophilic polymeric dispersant may be used in an amount of from 0.1 to 1 wt.%, or , preferably, 0.7 wt.% or less, or, preferably, 0.2 to 0.4 wt.%, based on the weight of the two-component aqueous compositions.
  • hydrophilic polymeric dispersant such as a polymethacrylic acid
  • the hydrophilic polymeric dispersant may be used in an amount of from 0.1 to 1 wt.%, or , preferably, 0.7 wt.% or less, or, preferably, 0.2 to 0.4 wt.%, based on the weight of the two-component aqueous compositions.
  • aqueous acid of the separate component is chosen from an alkanoic acid, such as, formic acid, acetic acid, propionic acid, butyric acid, an alkanedioic acid, such as succinic acid, adipic acid or malonic acid, a tricarboxylic acid, such as citric acid, and a polymeric polyacid, and is, preferably, an alkanoic acid.
  • aqueous acid of the separate component comprises from 0.1 to 30 wt.%, or, preferably, from 2.5 to 12 wt.% of acid in total, all amounts based on the total weight of the aqueous acid composition.
  • methods of making roof coatings comprise applying sequentially or by co-spraying to a roof substrate a two-component aqueous
  • each of the (i) one or more emulsion copolymers in component one has a weight average molecular weight of from 50,000 to
  • At least one of the (i) one or more emulsion copolymers in component one comprises, in copolymerized form, a monomer mixture of (a) from 60wt.% to 94 wt.%, preferably, 65 wt.% or more, or, preferably, up to 93.75 wt.% of one or more soft monomer, such as a C4 to C24 alkyl
  • (meth)acrylate for example, butyl acrylate or ethyl hexyl acrylate, (b) from 6.0 to 35 wt.%, preferably, 29.75 wt.% or less, or, preferably, up to 20 wt.%, of one or more hard vinyl monomers, such as a Ci to C3 alkyl (meth)acrylate, (meth) acrylonitrile or a vinyl aromatic monomer, preferably, methyl methacrylate (MMA) or acrylonitrile (AN), (c) from 0 to 3 wt.%, or, from 0.25 wt.% to 3.0 wt.% or, preferably, up to 2.75 wt.%, of one or more ethylenically unsaturated carboxylic acid group containing monomer, preferably, acrylic or methacrylic acid, or, more preferably, methacrylic acid, and, optionally, from (d) from 0 to 1 wt.%, or,
  • At least one of the (i) one or more emulsion copolymers in component one comprises, in copolymerized form, a monomer mixture of 19.5 wt.% or less or, preferably, 10 wt.% or less, or, more preferably, 5 wt.% or less of any vinyl aromatic monomer, such as styrene; and, further wherein, the monomer mixture comprises 1 1 wt.% or less or, preferably, 8 wt.% or less of (meth)acrylonitrile, all monomer wt.%s based on the total solids in the monomer mixture.
  • At least one of the (i) one or more emulsion copolymers in component one comprises, in
  • copolymerized form from 0.1 to 2 wt.%, based on the total solids in the monomer mixture, of an adhesion promoting ethylenically unsaturated monomer (e), such as a ureido functional
  • e adhesion promoting ethylenically unsaturated monomer
  • (meth)acrylate 15.
  • the component one further comprises one or more pigments, extenders, fillers or mixtures thereof, and has a pigment volume concentration (%PVC) of from 20 to 55 or, preferably, from 30 to 50, or, more preferably, 35 to 45.
  • %PVC pigment volume concentration
  • the component one further comprises one or more hydrophilic polymeric dispersant, such as a polymethacrylic acid; in one example, the total hydrophilic polymeric dispersant may be present in an amount of from 0.1 to 1 wt.%, or , preferably, 0.7 wt.% or less, or, preferably, from 0.2 to 0.4 wt.% based on the weight of the two-component aqueous compositions.
  • aqueous acid of the separate component is chosen from an alkanoic acid, such as, formic acid, acetic acid, propionic acid, butyric acid, an alkanedioic acid, such as succinic acid, adipic acid or malonic acid, or a tricarboxylic acid, such as citric acid, and a polymeric polyacid, and is, preferably, an alkanoic acid.
  • an alkanoic acid such as, formic acid, acetic acid, propionic acid, butyric acid
  • an alkanedioic acid such as succinic acid, adipic acid or malonic acid
  • a tricarboxylic acid such as citric acid
  • a polymeric polyacid is, preferably, an alkanoic acid.
  • aqueous acid of the separate component comprises from 0.1 to 30 wt.%, or, preferably, from 2.5 to 12 wt.% of total acid, all amounts based on the total weight of the aqueous acid composition.
  • the applying is continued until a coating having an average dry thickness of from 300 to 3,000 ⁇ , or , preferably, from 500 to 1 ,200 ⁇ m has been applied to the roofing substrate.
  • the total solids weight of the component one composition to the solids weight of acid in the separate composition ranges from 80:1 to 0.8:1 , or, more preferably, from 7:1 to 1 :1.
  • a disclosed proportion of 0.2 wt.% or more of hydrolysable silane, or up to 2.0 wt.%, preferably, 0.5 wt.% or more, or, preferably, 1.5 wt.% or less, or more preferably, 0.7 wt.% or more, based on the total weight of emulsion copolymer solids would include proportions of from 0.2 to 2.0 wt.%, or of from 0.2 to 1.5 wt.%, or of from 0.2 to 0.7 wt.%, or of from 0.2 to 0.5 wt.%, or of from 0.5 to 2.0 wt.%, or of from 0.5 to 1.5 wt.%, or of from 0.5 to 0.7 wt.%, or of from 0.7 to 2.0 wt.%, or of from 0.7 to 1.5 wt.%, or of from 1.5 to 2.0 wt.%.
  • glass transition temperature refers to the mid-point glass transition temperature of a polymer as determined by differential scanning calorimetry, measured using a DSC Q2000 (TA Instruments, New Castle, DE) in accordance with ASTM E-1356 (1991 ), wherein a given emulsion copolymer was dried over night at 60°C and then cooled to a temperature of -70 °C before scanning from -70 °C to 130 °C with a ramp rate of 20°C /minute. The results were averaged over two runs (original and a rescan run with a different sample of the same polymer).
  • the term "calculated Tg” or “calculated glass transition temperature” refers to the Tg of a polymer calculated by using the Fox equation (T. G. Fox, Bull. Am. Physics Soc, Volume 1 , Issue No. 3, page 123 (1956).
  • Fox equation T. G. Fox, Bull. Am. Physics Soc, Volume 1 , Issue No. 3, page 123 (1956).
  • a comprehensive compilation of available data describing glass transition temperatures of homopolymers from suitable monomers can be found in Polymer Handbook, Vol. 1 , editors Brandrup, J.; Immergut, E. H.; Grulke, E. A., 1999, pages VI/193-277.
  • coating thickness refers to an average of at least three measurements of a dried coating applied on a release paper roofing substrate, as measured using an Ames Gage, Model 13C-B2600 (Ames Corporation Waltham MA).
  • (meth)acrylate means acrylate, methacrylate, and mixtures thereof and the term “(meth)acrylic” used herein means acrylic, methacrylic, and mixtures thereof.
  • polymer refers, in the alternative, to a polymer made from one or more different monomer, such as a copolymer, a terpolymer, a tetrapolymer, a pentapolymer etc., and may be any of a random, block, graft, sequential or gradient polymer.
  • hard vinyl monomer means any monomer which would if polymerized to yield a homopolymer having a weight average molecular weight of 50,000 or greater form such a homopolymer with a glass transition temperature of 10 °C or more, or, preferably, 25 °C or more.
  • examples include (meth)acrylonitrile, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, and styrene.
  • soft monomer refers to any C4 to C24 alkyl (meth)acrylate monomer which would if polymerized to yield a homopolymer having a weight average molecular weight of 50,000 or greater form such a homopolymer with a glass transition temperature of -20 °C or less, or, preferably, -30 °C or less.
  • Examples include almost any C4 to C24 alkyl (meth)acrylate except t-butyl acrylate, n-hexadecyl acrylate and neopentyl acrylate, isobornyl acrylate, butyl methacrylate, and isobutyl methacrylate.
  • total emulsion copolymer solids refers to the copolymerized monomers, chain transfer agents, and surfactants in a given emulsion copolymer composition.
  • total solids in the monomer mixture refers to monomers as well as to reactive materials, such as chain transfer agents and the acids in the separate
  • total composition solids refers to any and every material in the two-component composition other than water, ammonia and volatile solvents.
  • the term “substantially zinc free” or “substantially multivalent transition metal ion free” refers to a composition containing less than 750 ppm, or, preferably, less than 500 ppm of zinc, whether in elemental form, i.e. as a metal, as an ion or as that portion of a compound that is itself zinc, such as the zinc in zinc oxide or its salt.
  • average particle size means a weight average particle size as determined by light scattering (LS) using a BI-90 particle size analyzer (Brookhaven Instruments Corp. Holtsville, NY).
  • weight average molecular weight refers to the weight average molecular weight as measured by aqueous gel permeation chromatography (GPC), using, for aqueous solution polymers (e.g. polymeric polyacids), polyacrylic acid (PAA) standards, and, for aqueous emulsion copolymers, polystyrene standards.
  • GPC gel permeation chromatography
  • two-component aqueous compositions can be applied in multiple passes giving a desired roof coating thickness in one application rather than in two or more applications.
  • the present inventors have surprisingly found that emulsion copolymer compositions containing one or more anionic surfactants can instantly form a homogenous film when combined during application with an organic acid or polymeric polyacid having carboxyl groups as a separate component.
  • the compositions are low odor compositions as well because there is no need to raise the pH of the coating or use volatile base to achieve cure.
  • low concentrations of relatively weak and inexpensive organic acids such as acetic acid or vinegar
  • the applied coating can be layered and sets within 10 seconds to 600 seconds, or preferably, in less than 60 seconds.
  • the set time can be reduced by any or all of increasing the amount of acid, by a co-spray application method, and by selecting a preferred type of acid allowing one to build multiple coating layers that can provide a suitable roof coating in a single application.
  • the two-component aqueous compositions enable formulation with conventional fillers, extenders and opacifiers (CaC03, T1O2, ZnO) as those materials do not significantly buffer the compositions or adversely affect the setting of the coating compositions.
  • the two-component aqueous compositions and methods of the present invention enable one to provide elastomeric white roof coatings in a single application.
  • aqueous emulsion copolymer compositions of component one comprise one or more anionic surfactant emulsion; and the separate component comprises aqueous acid to effect curing.
  • the amount of acid groups and the concentration of the acid will impact the rate of curing or setting.
  • the type and the concentration of the acid including the molecular weight of the acid and its pKa, will impact the rate of curing or setting.
  • concentration of aqueous acid can be used to control the setting process.
  • concentration of aqueous acid can be used to control the setting process.
  • effective as the separate component are:
  • a 10 to 25 wt.% solution of a polymeric polyacid a separate component of a 20 wt.% solution of a polyacrylic acid having a weight average molecular weight of about 2,700 provide an instantly non-deformable surface. Further, a 25 wt.% solution of the same polyacid was applied in a co-spray with an acrylic emulsion copolymer composition to provide a clear fluid with no deformation under the pressure of a hand touch. The combination of the two-component composition allowed for multiple passes in coating a roofing substrate and resulting in a homogenous film upon drying of 540 ⁇ in thickness.
  • the aqueous acid comprises an alkanoic acid or an alkanedioic acid in a 1 to 10 wt.% solution.
  • the aqueous emulsion copolymer of the present invention is copolymerized from a monomer mixture of one or more soft monomer (a) with one or more hard vinyl monomer (b), and, if desired, one or more ethylenically unsaturated carboxylic acid group containing monomer (c).
  • aqueous emulsion copolymer of the present invention can be prepared by emulsion polymerization techniques well known in the art for making emulsion copolymers from
  • hydrophobic soft monomers For example, U.S. Pat. No. 5,521 ,266 discloses suitable polymerization processes for suitable for forming emulsion copolymers made from one or more hydrophobic monomer, such as an alkyl (meth)acrylate having an alkyl group of from 8 to 24 carbon atoms, or, preferably, at least one such alkyl (meth)acrylate having an alkyl group of from 8 to 18 carbon atoms.
  • hydrophobic monomer such as an alkyl (meth)acrylate having an alkyl group of from 8 to 24 carbon atoms, or, preferably, at least one such alkyl (meth)acrylate having an alkyl group of from 8 to 18 carbon atoms.
  • the monomer can be complexed with a macromolecular organic compound having a hydrophobic cavity by mixing them to form a complexed mixture, and charging the complexed mixture, along with any other monomers to a reaction vessel.
  • a macromolecular organic compound having a hydrophobic cavity may be added to the reaction vessel before, during or after the monomer mixture has been charged.
  • Suitable macromolecular organic compounds having a hydrophobic cavity may include, for example, cyclodextrin and cyclodextrin derivatives; cyclic oligosaccharides having a hydrophobic cavity such as cycloinulohexose, cycloinuloheptose, and cycloinuloctose; calyxarenes; and cavitands.
  • the ratio of hydrophobic monomer to the macromolecular organic compound having a hydrophobic cavity may range from 1 :5 to 5000:1 , preferably 1 : 1 to 1000:1.
  • the polymerization of the aqueous emulsion copolymer of the present invention is catalyzed by an initiator, such as a peracid or its salt, for example, ammonium persulfate, or by a redox polymerization method which contains a reductant such as metabisulfite or sulfite salt.
  • an initiator such as a peracid or its salt, for example, ammonium persulfate
  • a redox polymerization method which contains a reductant such as metabisulfite or sulfite salt.
  • Such emulsion copolymers may be made by conventional methods, such as, for example, by including in the polymerization any of a wide variety of initiators, such as thermal (e.g.
  • the chain transfer agent is hydrophobic, such as n-dodecyl mercaptan (n-DDM or DDM) or any C4 to C18 mercaptan.
  • Suitable conventional aqueous emulsion polymerization methods for making emulsion copolymers may include, for example, polymerizing in the presence of from 0.01 to 1 wt.%, based on the total weight of monomers used to make the copolymer, of one or more
  • surfactants or, preferably, in the presence of small amounts of surfactant, such as, for example, from 0.01 to 0.4 wt.%, based on the total weight of monomers used to make the copolymer, preferably, 0.08 to 0.32 wt.%.
  • Anionic surfactants are preferably used.
  • a monomer mixture is selected to give a desired Tg.
  • the monomer components of the aqueous emulsion copolymer should be selected such that the Tg of the dried copolymer is from -45 °C to 0 °C, and, preferably, from -30°C. to -10°C.
  • Polymers having Tg's above 0°C yield coatings which may lose their flexibility at low temperature.
  • Polymers having Tg's of -50°C or below are prone to tack issues, low tensile strength, and bleed-through of colored chemicals from substrate into coatings thereon, thereby deteriorate the performance of the coatings.
  • Suitable soft monomers for use as monomer (a) of the present invention may include, for example, a C4 to C6 alkyl (meth)acrylate monomer, such as, for example, n-butyl acrylate (BA), iso-butyl acrylate; a C7-C24 alkyl or alkylaryl (meth)acrylate monomer, such as, for example, ethylhexyl acrylate (EHA), octyl methacrylate, isooctyl methacrylate, decyl methacrylate (n- DMA), isodecyl methacrylate (IDMA), lauryl methacrylate (LMA), pentadecyl methacrylate, stearyl methacrylate (SMA), octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate (LA), the (C12
  • Suitable hard vinyl monomers (b) may include, for example, (meth)acrylic ester monomers including Ci to C3 alkyl (meth)acrylates, such as methyl methacrylate (MMA), ethyl
  • (meth)acrylate Ci to C20 cycloaliphatic (meth)acrylates, such as isobornyl methacrylate and cyclohexyl methacrylate; vinyl aromatics, such as styrene, alkylstyrenes (methyl and ethyl), like alpha methyl styrene; (meth)acrylonitrile; (meth)acrylamide or substituted (meth)acrylamides.
  • (meth)acrylamide or substituted (meth)acrylamides used as a hard vinyl monomer ranges up to 2.5wt.%, or, preferably, up to 1.25wt.%, based on the total solids in the monomer mixture.
  • the aqueous emulsion copolymer may include carboxylic acid functionality by way of (c) an ethylenically unsaturated carboxylic acid group containing monomer, such as, for example, maleic acid or anhydride, itaconic acid or, preferably, methacrylic acid (MAA) and acrylic acid (AA).
  • carboxylic acid functionality by way of (c) an ethylenically unsaturated carboxylic acid group containing monomer, such as, for example, maleic acid or anhydride, itaconic acid or, preferably, methacrylic acid (MAA) and acrylic acid (AA).
  • any acrylic acid is added in a polymer seed or in an initial charge to a
  • ethylenically unsaturated acid monomers (d) may be used in amounts of up to 1.2 wt.%, or, preferably, up to 0.8 wt.%, all monomer wt.%s, based on the total solids in the monomer mixture, and include acids with sulfur acid functionality and phosphorus acid monomers.
  • Suitable ethylenically unsaturated sulfur containing acid functional monomers may include, for example, sodium styrene sulfonate (SSS), and (meth)acrylamidopropane sulfonate.
  • suitable phosphorus acid monomers may include, for example, phosphoalkyl (meth)acrylates such as phosphoethyl methacrylate.
  • the aqueous emulsion copolymer comprises the reaction product of less than 2 wt.%, or, more preferably, less than 0.5 wt.%, based on the total solids in the monomer mixture of a multi-ethylenically unsaturated monomer.
  • the resulting emulsion copolymer is more linear and has greater elongation %.
  • the emulsion copolymer comprises from 0.1 to 6 wt.%, preferably, 0.5 to 5 wt.%, based on the total solids in the monomer mixture, of acetoacetoxyethyl methacrylate.
  • a very low level e.g. up to 0.8 wt.%, based on total solids in the monomer mixture
  • one or more sulfur acid monomer (d) acts as an in-process stabilizer to significantly reduce gel formation during synthesis without hurting water resistance properties, and has no significant negative effect on water swelling.
  • the sulfur acid monomer could be used to enhance polymerization.
  • the aqueous emulsion copolymer of the present invention comprises the copolymerizate of one or more adhesion promoting ethylenically unsaturated monomers (e), such as an ethylene ureido functional ethyl methacrylate monomer.
  • suitable monomers include ureidoalkyl (meth)acrylates, ureidoalkyl (meth)acrylamides and other ureido group containing monomers such as, for example, those disclosed in U.S. Patent no. 3,356,627 to Scott.
  • Polymerizable surfactant monomers may be used in the monomer mixture of the present invention in amounts of up to 1 wt.%, based on the total solids in the monomer mixture, to increase the potential scope of monomer mixtures useful to make the emulsion copolymers of the present invention.
  • Suitable such monomers may include styrenated phenol sulfates, such as those available as HitenolTM BC-1025 (Montello inc., Tulsa, OK), AerosolTM NPES - 930
  • E-SperseTM RS-1596 and E-SperseTM RS- 1618 comprising a styrenated phenol hydrophobe with 2 equivalents of allyl glycidyl ether ethoxylated with 15 moles or ethylene oxide, sulfated and neutralized (Ethox Chemicals, Greenville, SC) and sodium dodecylallyl sulfosuccinate such as TREMTM LF-40 (Cognis, Cincinnati, OH).
  • chain transfer agents such as, for example, alkyl mercaptans, halogen compounds may be used.
  • the chain transfer agent is hydrophobic, such as n-dodecyl mercaptan (n-DDM or DDM) or any C4 to C18 mercaptan.
  • chain transfer agents such as, for example, n-dodecylmercaptan should be used in amounts ranging from 0 wt.%, or 0.01 wt.%, based on the weight of total solids in the monomer mixture, to 0.3 wt.%, or, more preferably, 0.2 wt.% or less, or, more preferably, 0.1 wt.%, or less.
  • Use of such low amount of the CTA in an emulsion copolymer avoids an increase in water swell or a decrease in elongation in coatings made from the emulsion copolymers.
  • the aqueous emulsion copolymer of the present invention may have a weight average particle size of from 80 to 500 nm, such as, for example, a relatively large particle size of from 200 to 500 nm which improves adhesion and increases the critical %PVC of compositions containing them, i.e. the non-binder loading capacity of the coating compositions.
  • large particle size emulsion copolymers may be formed by, for example, polymerizing the monomer mixture under low shear during polymerization.
  • use of an amount of surfactant below 0.4 wt.%, based on the total weight of monomers, may improve the water resistance of coatings or films made from the coating compositions.
  • Suitable aqueous emulsion copolymers have a weight average molecular weight of 50,000 to 2,000,000, preferably 150,000 or more, or, preferably, 500,000 or less.
  • use of emulsion copolymers of such a molecular weight enable an increase in the critical %PVC of compositions containing them.
  • the monomer mixture is subject to gradual addition emulsion polymerization.
  • Another suitable aqueous emulsion polymerization method comprises shot polymerization with up to 0.2 wt.% of total nonionic and anionic surfactants or just anionic surfactants, based on the total solids in the monomer mixture and a preferred level of chain transfer agent.
  • Additional anionic surfactant (ii) can be added to the aqueous emulsion copolymers of the present invention after polymerization.
  • Total amounts of anionic surfactant in component one of the present invention should range from 0.1 to 6 wt.%, or, preferably, from 0.1 to 0.4 wt.%, based on total emulsion copolymer solids.
  • Suitable anionic surfactants may include, for example, sulfate containing surfactants, such as sodium lauryl sulfate, sulfonate containing surfactants sodium dodecylbenzene sulfonate, and sulfosuccinate containing surfactants, such as dioctyl or dihexyl sulfosuccinates.
  • the solids level of the aqueous component one compositions of the present invention may range 15 wt.% or higher and up to 80 wt.%, preferably, 40 wt.% or higher, or, more preferably, 50 wt.% or higher, or, even more preferably, 60 wt.% or higher, all wt.%s based on the total solids of the compositions, including any fillers, extenders and pigments and any solid additive present in a coating or film made from the compositions.
  • the two-component aqueous compositions of the present invention have a VOC content of 100 g/L or less, preferably, 50 g/L or less.
  • the aqueous component one compositions of the present invention can have a pigment volume concentration (%PVC) of from 20 to 55 or, preferably, 30 to 50, or, more preferably, from 35 to 45.
  • %PVC pigment volume concentration
  • Total volumes of pigment, extender and/or opacifier in excess of 50 %PVC will impair elongation, whereas a lack of sufficient volume of such material can impair tensile strength of a coating made from the aqueous compositions of the present invention.
  • the two-component compositions of the present invention may comprise conventional fillers and processing aids for elastomeric roof coatings, so long as the amount of ammonia and added salt is limited to within the desired levels.
  • the component one of the present invention is pigmented and also contain extenders or fillers.
  • Suitable pigments may be opacifiers, for example, titanium dioxide, hollow sphere or void containing or polymer pigments; iron oxides, IR reflective pigments or zinc oxide.
  • Suitable extenders may be, for example, calcium carbonate, clay, mica, talc, alumina silicates, aluminum trihydrate, nepheline syenite or mixtures of any of these with other extenders. Fillers and extenders are considered the same thing.
  • the component one of the present invention comprises one or more extenders, such as calcium carbonate, and one or more pigments, such as titanium dioxide, or iron oxide.
  • Clearcoat compositions may be formulated with extenders and no pigments.
  • the aqueous component one compositions of the present invention may be, for example, substantially zinc free or substantially multivalent transition metal ion free which retain good water swell and dirt pick up resistance performance in coatings, the compositions having a %PVC of 43 or higher and comprising emulsion copolymers having a Tg of from -30 to -10 °C, wherein the monomer mixture from which the emulsion copolymer is made comprises
  • (meth)acrylonitrile in the amount of from 0.5 to 8 wt.%, a Ci to C3 alkyl (meth)acrylate, preferably methyl methacrylate, in the amount of from 8 to 20 wt.%, or their combination, all monomer wt.%s based on the total solids in the monomer mixture.
  • the component one compositions of the present invention may also comprise one or more hydrophilic polymeric dispersant, such as a polymethacrylic acid, or a polyacid salt, e.g.
  • alkali(ne) metal salt for example, polyMAA, its Na salt.
  • Any hydrophilic dispersant that can stabilize pigments, extenders and/or fillers and wet out substrate surface in use may be used, such as, for example, copolymer dispersants like TamolTM 851 (Na poly(MAA)) or 1 124
  • poly(AA-co-hydroxypropyl acrylate)) dispersants (Dow Chemical, Midland, Ml), or RhodolineTM 286N dispersants (Rhodia, Cranbury, NJ), hydrophilic copolymer acid salts, alkali soluble polymer or resin salts, and phosphoethyl methacrylate (PEM) polymer and copolymer dispersants.
  • POM phosphoethyl methacrylate
  • Suitable hydrophilic polymeric dispersants may contain the polymerization product of less than 30 wt.%, or, preferably, 20 wt.% or less, based on the total weight of monomers used to make the copolymers, of monomers like alkyl (meth)acrylates, dienes or olefins other than hydrophilic acid monomers.
  • Preferred hydrophilic dispersants may have a weight average molecular weight of 5,000 or more, preferably 8,500 or more.
  • Hydrophilic polymeric dispersants do not include emulsion copolymer dispersants or block copolymer dispersants comprising more than 20 wt.%, based on the total weight of
  • copolymerized monomers of a block that would not form a water soluble homopolymer (>50g/L dissolves at room temp upon mixing) at the weight average molecular weight of the dispersant block in use.
  • a block of a monomer in a block copolymer has a weight average molecular weight of 1 ,000 in the dispersant, then a homopolymer having a weight average molecular weight of 1 ,000 of the same monomer used to make the block in the dispersant is evaluated to see if it is water soluble.
  • hydrophilic dispersants should be used in amounts of 2 wt.% or less, based on the total pigment, filler and extender solids in the component one compositions.
  • compositions comprising one or more hydrolysable silanes or alkoxy silanes, which preferably have two or three hydrolysable groups.
  • Suitable amounts of epoxysilane, aminosilane, vinyl alkoxysilane are the same. Combinations of the epoxysilanes and aminosilanes may be used.
  • Suitable aminosilanes may comprises an amino-alkyl functional group and is hydrolysable, having, for example, one or more alkoxy group or aryl(alkyl)oxy functional group.
  • the amino silane has two or more amino functional groups and two or, more preferably, three hydrolysable groups, i.e. tri-alkoxy.
  • Suitable aminosilanes include MomentiveTM SilquestTMA-1120 (Momentive
  • silanes include, for example, MomentiveTM SilquestTMA-174 which is methacryloxypropyltrimethoxysilane, Dow Corning Z-6040 (Dow Corning, Midland, Ml), which is glycidoxypropy trimethoxysilane, and
  • Silanes may be used in amounts ranging from 0.2 wt.% or more, or up to 2.0 wt.%, preferably, 0.5 wt.% or more, or, preferably 1.5 wt.% or less, or, more preferably, 0.7 wt.% or more, based on the total weight of emulsion copolymer solids in the component one
  • the component one compositions of the present invention may additionally comprise one or more of thickeners, such as hydroxyethylcellulose (HEC) or modified versions thereof, UV absorbers, surfactants, coalescents, wetting agents, thickeners, rheology modifiers, drying retarders, plasticizers, biocides, mildewicides, defoamers, colorants, waxes, and silica.
  • thickeners such as hydroxyethylcellulose (HEC) or modified versions thereof, UV absorbers, surfactants, coalescents, wetting agents, thickeners, rheology modifiers, drying retarders, plasticizers, biocides, mildewicides, defoamers, colorants, waxes, and silica.
  • the component one compositions may preferably include one or more UV absorber or light stabilizer, such as benzophenone (BZP), or butylated hydroxytoluene (BHT) or hindered amines in the total amount of from 0 to 1 wt.%, based on the total solids of the composition, preferably, 0.05 wt.% or more or up to 0.5 wt.%.
  • UV absorber or light stabilizer such as benzophenone (BZP), or butylated hydroxytoluene (BHT) or hindered amines in the total amount of from 0 to 1 wt.%, based on the total solids of the composition, preferably, 0.05 wt.% or more or up to 0.5 wt.%.
  • the compositions of the present invention comprise no or substantially no (350 ppm or less) benzophenone but retain the same good dirt pick up resistance in coatings as those made from compositions which contain 0.3 wt.%, based on total two-component composition solids, of benzophenone.
  • the aqueous component one compositions of the present invention may be prepared by mixing the elastomeric aqueous emulsion copolymer with conventional components in high speed dispersion equipment such as a Cowles disperser, or a Sigma mill for caulks and sealants.
  • the silane can be added with stirring, such as overhead stirring, preferably before pigments, fillers or extenders are added.
  • the pigmented two-component compositions of the present invention are suitable for making white roof coatings or white roof maintenance coatings.
  • compositions of the present invention are preferably used as topcoats or topcoat maintenance coatings, especially if formulated with UV absorbers or light stabilizers, or can be used as the basecoat or maintenance basecoats in two coat system, e.g. with the same or different topcoat or mastic.
  • substrates can be prepared for coating with cleaning or treatment by physical abrasion, flame ionization, powerwashing with water, applying an aqueous cleaning solution, such as, for example, from 5 to 10 wt.% trisodium phosphate, or other cleaning agents, followed by powerwashing with water, or plasma treatment prior to coating.
  • aqueous cleaning solution such as, for example, from 5 to 10 wt.% trisodium phosphate, or other cleaning agents
  • the compositions formulations of the present invention preferably are substantially free of zinc oxide, zinc containing additives or zinc ions.
  • Zinc reduces the adhesion of the coating to weathered TPO.
  • the compositions are substantially zinc free and contain less than 750 ppm of Zn, whether as metal, ions or as that portion of a compound that is itself zinc, the weight based on the total solids of the composition, preferably less than 100 ppm.
  • the two-component compositions of the present invention can be used on any roofing substrates to form a roof coating.
  • the two-component compositions of the present invention may be applied to a wide variety of weathered and unweathered roofing substrates, such as, for example, asphaltic coatings, roofing felts, synthetic polymer membranes; foamed polyurethane, for example, spray polyurethane foam; and metals, such as aluminum; thermoplastic polyolefins (TPO), silicone rubber and ethylene propylene diene rubber (EPDM) or to previously painted, primed, undercoated, worn, or weathered substrates, such as metal roofs, weathered TPO, weathered polyvinyl chloride) (PVC), weathered silicone rubber and weathered EPDM rubber.
  • TPO thermoplastic polyolefins
  • EPDM ethylene propylene diene rubber
  • PVC polyvinyl chloride
  • Other suitable substrates include modified bitumen membrane.
  • BA butyl acrylate, LMA: lauryl methacrylate; MMA: methyl methacrylate; STY: styrene; AN: acrylonitrile; MAA: methacrylic acid; Ureido: ethylene ureido functional ethyl methacrylate monomer; DDBS: sodium dodecyl benzene sulfonate; SLS; sodium laureth sulfate; ANS: ammonium nonoxynol-4 sulfate; Seed: BA-MMA seed polymer (100 nm average particle size) emulsion copolymer 1 : A 55 wt.% solids, single stage copolymer having a pH of 9, a DSC glass transition temperature (Tg) of -26.33 °C, made from (by solids weight%) 85.1 BA/12.3 MMA/1.6 MAA/1 Ureido with 2.2 wt.% Seed and 0.11 wt.% DDBS, and
  • emulsion copolymer 2 A 55 wt.% solids, single stage copolymer having a pH of 8, a DSC Tg of -10.2 °C, made from (by solids weight%) 70.3 BA/27 STY/2.7 MAA with 2.0 wt.% Seed, 0.25 wt.% SLS and 0.20 wt.% ANS, and containing 0.13 wt.% ammonia;
  • hydrophilic dispersant polymethacrylic acid sodium carboxylate, 30 wt.% in water;
  • TamolTM 681 dispersant (Acrylic copolymer, 37-38 wt.% solids in water and propanediol, The Dow Chemical Company, Midland, Ml (Dow);
  • DEEFOTM 1015 defoamer (Petroleum distillates, solvent dewaxed heavy paraffinic CAS#64742-65-0 >50%, Munzing, Bloomfield NJ);
  • rutile titanium dioxide Ti-PureTM R-960 titanium dioxide (Chemours, Wilmington DE);
  • ZocoTM 101 zinc oxide, Zochem Inc., Brampton, Ontario, CA
  • KTPP potassium tripolyphosphate (ICL Performance Products, Trenton NJ);
  • coalescent 1 odorless mineral spirits or OMS
  • HEC thickener CellosizeTM QP-52000 hydroxyethyl cellulose (HEC thickener, Dow); coalescent 2: UCARTM Filmer (2,2,4-trimethyl-1 ,3-pentanediol mono(2-methylpropanoate) CAS#:25265-77-4, Dow);
  • aqueous ammonia (28 wt.%, Fisher Scientific, St. Louis, MO); and,
  • polymeric polyacid Polyacrylic acid with a weight average molecular weight of 2,700.
  • Test Methods The following test methods are used in the Examples.
  • Coating hardness after the 10 second setting period in the test is improved more by using the preferred aqueous (poly)carboxylic acid separate component than by the aqueous polymeric polyacid.
  • Ammonia was not involved in the setting of the coatings because less than 0.06 wt.% of the coating compositions contain ammonia.
  • a 25 wt.% aqueous solution of polyacrylic acid with a weight average molecular weight of 2,700 was co-sprayed with coating Example 2 making 3 passes on a piece of polysiloxane coated release paper (Leneta Release Paper RP-1 K 219 mm x 286 mm (8 5/8 x 11 1 ⁇ 4 inch)) Mahwah, NJ).
  • the dry film thickness of the coating was 540 ⁇ m.

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EP16816476.2A 2015-11-25 2016-11-21 Wässrige zweikomponentenzusammensetzung zum beschichten von dachuntergründen und verfahren zur herstellung von dachbeschichtungen Active EP3380561B1 (de)

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US3356627A (en) 1963-06-17 1967-12-05 Rohm & Haas Aqueous blends of two water-insoluble polymers, one of which has 1 to 15% of a monomer containing an alcoholic hydroxyl, amino, amido or ureido group
US5521266A (en) 1994-10-28 1996-05-28 Rohm And Haas Company Method for forming polymers
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US5985366A (en) 1995-02-27 1999-11-16 Wright; Winfield S. Sprayable roof coating systems
US7402627B2 (en) * 2003-08-18 2008-07-22 Columbia Insurance Company Precursor colorant composition for latex paint
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US10053597B2 (en) * 2013-01-18 2018-08-21 Basf Se Acrylic dispersion-based coating compositions
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